Pyridyloxy-phenoxyalkanecarboxylic acid derivatives

ABSTRACT

Herbicidal and plant growth-regulating pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula ##STR1## wherein A is cyano or carboxyl, an ester, thioester or amido radical or the salt of the carboxylic acid with a cation or a quaternary ammonium group, 
     Z is hydrogen, halogen, cyano, nitro, C 1  -C 4  alkyl or C 1  -C 4  alkoxy, 
     D is hydrogen, halogen, cyano, nitro or C 1  -C 4  alkoxy, 
     E is halogen, trifluoromethyl or cyano. 
     R 1  is hydrogen, C 1  -C 4  alkyl, C 2  -C 8  alkoxyalkyl or C 1  -C 5  alkoxy carbonyl and 
     R 2  is hydrogen or C 1  -C 4  alkyl

CROSS-REFERENCE TO RELATED APPLICATION

This is a continuation-in-part of our application, Ser. No. 080,965, filed Oct. 1st, 1979 which is a continuation of our application, Ser. No. 919,119, filed June 26th, 1978, both now abandoned.

DETAILED DISCLOSURE

The present invention relates to novel pyridyloxy-phenoxyalkanecarboxylic acid derivatives which have a herbicidal and plant growth-regulating action, processes for their production, compositions which contain these compounds as active ingredients, and to a method of selectively controlling weeds and of regulating plant growth which comprises the use of the novel active substances or of compositions which contain them.

The active compounds of the present invention have the formula I ##STR2## wherein A represents the cyano group, a radical --COB or a 2-oxazoline radical which is unsubstituted or mono- or polysubstituted by methyl,

B represents a radical --OR₃, --SR₃, --NR₄ R₅ or --O--N═C (C₁ -C₄ alkyl)₂

Z and D each individually represent hydrogen, halogen, cyano, nitro, C₁ -C₄ alkyl or C₁ -C₄ alkoxy,

E represents halogen, trifluoromethyl, cyano or nitro,

R represents hydrogen, C₁ -C₄ alkyl or C₂ -C₈ alkoxyalkyl, or C₁ -C₅ alkoxycarbonyl

R₂ represents hydrogen or C₁ -C₄ alkyl,

R₃ represents hydrogen, ammonium or an alkali or alkaline earth metal cation, a benzyl or C₁ -C₄ alkylammonio group, whose alkyl radicals may be substituted by hydroxyl C₁ -C₄ alkoxy or

a C₁ -C₁₈ alkyl radical which is unsubstituted or substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxyalkoxy, C₂ -C₈ alkoxycarbonyl, bis(C₁ -C₄ alkyl)amino, C₃ -C₈ cycloalkyl, C₃ -C₈ cycloalkenyl and also by a 5 to 6-membered heterocyclic radical which is unsubstituted or is itself mono- or polysubstituted by C₁ -C₄ alkyl;

a C₃ -C₁₀ alkenyl radical which is unsubstituted or mono- or tetrasubstituted by halogen;

a C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl- or C₃ -C₈ cycloalkenyl radical;

a phenyl or benzyl radical, which is mono- or polysubstituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, C₁ -C₄ alkylthio, nitro, trifluoromethyl, cyano, carboxyl, sulfonyl, hydroxyl, amino or bis(C₁ -C₄ alkyl)amino;

a 5 to 6-membered heterocyclic radical;

R₄ represents hydrogen, a C₁ -C₈ alkyl radical, unsubstituted or substituted by halogen, hydroxyl, cyano, C₁ -C₄ alkoxy or C₁ -C₄ alkoxycarbonyl;

C₃ -C₈ alkenyl, unsubstituted or halogensubstituted;

C₃ -C₈ alkynyl, C₃ -C₈ cycloalkyl or C₃ -C₈ cycloalkenyl;

phenyl or benzyl, unsubstituted or substituted by halogen, C₁ -C₄ alkyl, C₁ -C₄ alkoxy, trifluoromethyl, nitro or cyano;

R₅ represents the same as R₄ or C₁ -C₄ alkoxy or C₂ -C₄ alkenyloxy or

R₅ and R₆ together with the nitrogen atom, to which they are attached, form also a 5 to 6-membered heterocyclic ring, which may be substituted by C₁ -C₄ alkyl.

In the above formula the alkyl radicals can be branched or unbranched and contain the indicated number of carbon atoms. The heterocyclic radicals R₃ include, furyl-, tetrahydrofuryl-, oxane-, thiophene-radicals and further, the same that are also found by the symbols R₄ and R₅ with the nitrogen to which they are attached, pyrrolidine, pyridine, piperidine, morpholine, oxazoline or piperazine. These rings may be substituted by C₁ -C₄ alkyl radicals.

The active compounds of the formula (I) of the present invention possess a herbicidal action, especially in post-emergent application, and can be used as weed-killers in crops of mono- and dicotyledonous plants. They also possess advantageous growth-regulating effects (growth inhibition). In particular, they inhibit the growth of dicotyledonous plants. Exemplary of the useful application of the compounds of the present invention are:

the reduction of the vegetative growth in soya and similar leguminosae, resulting in an increase in the yield of these plants;

the inhibition of the undesirable growth of suckers in tobacco plants, the leading shoots of which have been cut, thus promoting the formation of larger and finer leaves;

the inhibition of the growth of grass and dicotyledonous plants, such as fruit trees, ornamental trees, bushes and hedgerows, with the object of saving cutting work.

The compounds of the present invention have a low toxicity to warm-blooded animals and their application causes no problems. The rate of application is between 0.1 and 5 kg per hectare.

Good herbicidal activity has been observed with the groups of compounds listed below. They are therefore of special interest among the compounds of formula I. ##STR3##

In these formulae, B has the meanings given above under formula I.

From the U.S. Pat. Nos. 4,046,553 and 4,105,435 have become know 4-pyridyloxy-phenoxyalkanecarboxylic acid derivatives with herbicidal activity. The compounds of this invention proved to act differently and are capable of controlling plants, which were not or not satisfactorily controlled with compounds known from these patents.

The novel compounds of the formula (I) can be obtained by processes which are in themselves known. In a first process, a substituted or unsubstituted halopyridine of the formula II, ##STR4## wherein D and E are as defined in formula (I) and Hal represents a halogen atom, preferably a chlorine or bromine atom, is reacted with a hydroxyphenoxyalkanecarboxylic acid derivative of the formula III, wherein A, Z, R₁ and R₂ are as defined in formula (I), in the presence of an acid acceptor.

Such reactions are in themselves known and the exact method by which they are carried out is described in the literature, for example in Houben-Weyl, Volume 3, page 85 ff.

In a second process, the pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula (I) are prepared by reacting a pyridyloxy-hydroxyphenyl ether of the formula IV, ##STR5## wherein Z, D and E are as defined in formula (I), with an α-halogenocarboxylic acid derivative of the formula V ##STR6## wherein A, R₁ and R₂ are as defined in formula (I) and Hal represents a halogen atom, preferably a chlorine or bromine atom, in the presence of an acid acceptor.

The above reactions can be carried out in the presence or absence of solvents or diluents which are intert to the reactants. Polar organic solvents, such as methyl ethyl ketone, acetonitrile, dimethyl formamide, dimethyl sulphoxide etc., are preferred. The reaction temperatures are between 0° and 200° C. and the reaction time is from 1/4 hour to several days, depending on the chosen reaction temperature and solvent. The reaction is ordinarily carried out under normal pressure or slight excess pressure. Suitable acid acceptors for the reaction are inorganic bases, for example NaOH, KOH, NaOCH₃, NaH, K₂ CO₃, potassium tert-butylate etc., and also organic bases.

A number of the starting materials of the formulae (II) to (V) are known. Starting materials of these formulae which have not yet been described can be easily prepared by conventional processes and techniques.

Substituted 2-halogeno-pyridines of the formula (II) can be easily obtained from the corresponding 2-pyridinoles, some of which are known. Starting materials of the formula (III) can be obtained by reacting, for example, a monobenzyl ether of an optionally substituted resorcinol with an α-halogenocarboxylic acid derivative, preferably an ester of the formula (V), and cleaving the benzyl-phenyl ether bond by catalytic hydrogenation, for example with a palladium on carbon catalyst, whereby the benzyl radical is removed as toluene.

The starting materials of the formula (IV) can be obtained by reaction of resorcinol with halopyridines in equimolar amounts and in the presence of a base.

Carboxylic acid derivatives of the formula (V) are also known. As their simplest representatives, mention may be made for example of chloroacetic acid and the esters, thioesters and amides thereof. However, other α-halocarboxylic acid derivatives substituted in accordance with R₁ and R₂ are also suitable.

The following Examples illustrate the process of the present invention for obtaining arbitrarily chosen active compounds of the formula (I). Further active compounds which are obtained in corresponding manner are listed in the subsequent tables.

These pyridyloxy-phenoxyalkanecarboxylic acid derivatives of the formula (I) are stable compounds which are soluble in conventional organic solvents, such as alcohols, ethers, ketones, dimethyl formamide, dimethyl sulphoxide etc.

EXAMPLE 1 α-[3-(3',5'-Dichloropyrid-2-yl)-oxy-phenoxy] propionic acid methyl ester (intermediate) ##STR7##

30.8 g (0.1 mole) of 3-(3',5'-dichloropyrid-2'-yl)-oxy-phenoxy phenol, 18.2 g (0.13 mole) of potassium carbonate and 22 g of methyl α-bromopropionate are refluxed in 300 ml of ethyl ketone for 3 hours. The inorganic salts are then filtered off and the filtrate is concentrated. Recrystallisation of the residue from ether/petroleum ether affords 29 g (70% of theory) of the title product with a melting point of 58°-60° C.

EXAMPLE 2 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionic acid methyl ester ##STR8##

(a) 171 g (0.5 mole) of α-[3-(3',5'-dichloropyrid-2-yl)oxy-phenoxy] propionic acid (prepared according to Example 1) are dissolved in 250 ml of 1,2 dichloroethane. The reaction is then cooled to -12° to -14° C. and during 2 hours there is added dropwise 250 ml of 100% nitric acid. After 1/2 hour, the reaction mixture is poured into ice-water. The mixture is then extracted methylene chloride. The organic phase is washed twice with water, dried over magnesium sulfate and evaporated. The residue is taken up in 500 ml of hexane and triturated, which causes it to crystallise. The cristals are filtered and dried to yield 172.3 g (89% of theory) of the title compound which melts at 107°-108° C.

This compound can also be produced in the following manner.

(b) 30.1 g (0.1 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenol, 16.7 g (0.1 mole) of methyl α-bromopropionate and 20.7 g (0.15 mole) of potassium carbonate are refluxed for 14 hours in 400 ml of methyl ethyl ketone. The inorganic salts are filtered off and the filtrate is concentrated. The residual brown oil is taken up in chloroform and filtered over a short column of silica gel, affording 22.4 g (58% of theory) of title product which melts at 107° C. after recrystallisation from hexane.

EXAMPLE 3 3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenyl acetate (intermediate)

A mixture of 256 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.9 liters of glacial acetic acid and 280 ml of acetic anhydride is stirred for 12 hours at reflux temperature. The solution is cooled to 40° C., then 81 g of sodium acetate are added with stirring and 106 g of chlorine gas are introduced at 40° C. in the course of 7 hours. Excess chlorine gas is removed by introducing nitrogen for 2 hours and the solution is concentrated. The ethyl acetate solution (1000 ml) of the oily residue is washed with water and saturated NaHCO₃ solution and concentrated, affording 343 g of the title compound as a brown oil which crystallises spontaneously on trituration with petroleum ether. Melting point: 71°-75° C.

EXAMPLE 4 3-(3',5'-Dichloropyridyl-2'-oxy)-6- and 4-chlorophenol (intermediate)

A suspension of 2.26 g of powdered KOH and 10 g of 3-(3',5'-dichloropyridyl-2'-oxy)-6-phenyl acetate in 30 ml of absolute methanol is stirred for 20 minutes at 60° C. in a nitrogen atmosphere, cooled to room temperature, acidified with 3.7 ml of concentrated hydrochloric acid and concentrated. The toluene solution (50 ml) of the residue is washed with water, dried, filtered over activated carbon and concentrated, affording 8.4 g of an oil which consists of a mixture of the 6-chlorophenol and 4-chlorophenol isomers in the ratio 7:3.

EXAMPLE 5 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid methyl ester ##STR9##

25 g (0.085 mole) of a mixture of 3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenol and 3-(3',5'-dichloropyridyl-2'-oxy)-4-chlorophenol (prepared according to Example 4), 14.2 g (0.085 mole) of methyl α-bromopropionate and 13.8 g (0.1 mole) of potassium carbonate are refluxed for 6 hours in 250 ml of methyl ethyl ketone. The inorganic salts are filtered off and the filtrate is concentrated. The residual yellow oil is recrystallised from ether/petroleum ether, affording 30.1 g (94% of theory) if isomer-free title product with a melting point of 82°-83° C.

EXAMPLE 6 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenyl acetate (intermediate)

A mixture of 205 g of 3-(3',5'-dichloropyridyl-2'-oxy)-phenol, 1.1 liters of glacial acetic acid and 224 ml of acetic anhydride is stirred for 12 hours at reflux temperature. The solution is cooled to 60° C., then 64.8 g of sodium acetate are added with stirring and a solution of 102 ml of bromine in 400 ml of glacial acetic acid are added dropwise at 60° C. in the course of 53/4 hours. The solution is concentrated and the residue is dissolved in ethyl acetate. The organic phase is washed in succession with water and saturated NaHCO₃ solution. The combined ethyl acetate extracts are dried and concentrated, affording 302.5 g of an oil which crystallises on being covered with a layer of petroleum ether (b.p. 60°-90° C.) After recrystallisation from cyclohexane, the title product melts at 106°-107° C.

EXAMPLE 7 3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenol (intermediate)

A suspension of 28 g of powdered KOH and 153.5 g of 3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenyl acetate in one liter of absolute methanol is stirred for 20 minutes at 60° C. in a nitrogen atmosphere and concentrated. The concentrate is acidified at room temperature with concentrated hydrochloric acid and evaporated to dryness. The toluene solution (400 ml) of the residue is washed with water, dried, and concentrated. The oily residue is triturated with petroleum ether/cyclohexane and filtered, affording 137 g of the crystalline title product with a melting point of 93°-95° C.

EXAMPLE 8 α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy] propionic acid methyl ester ##STR10##

50.2 g (0.15 mole) of 3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenol (prepared according to Example 7), 27.5 g (0.165 mole) of methyl α-bromopropionated and 27.6 g (0.2 mole) of potassium carbonate are refluxed for 5 hours in 250 ml of methyl ethyl ketone. The inorganic salts are filtered off and the filtrate is concentrated. The residual reddish oil is recrystallised from ether/petroleum ether, affording 58 g (91.8% of theory) of the title compound with a melting point of 75° C.

Analogously to these Examples, the following compound can be prepared:

    ______________________________________                                          ##STR11##                                                                     No.         B               phys. data                                         ______________________________________                                         1         OCH.sub.3         m.p. 82-83°                                 2         OC.sub.2 H.sub.5  m.p. 53-56°                                 3         OC.sub.3 H.sub.7 iso                                                                             n.sub.D.sup.25 1.5567                              4         OC.sub.3 H.sub.7 n                                                   5         OC.sub.4 H.sub.9 n                                                                               n.sub.D.sup.25 1.5540                              6         OC.sub.4 H.sub.9 sec.                                                                            n.sub.D.sup.25 1.5525                              7         OC.sub.4 H.sub.9 tert.                                               8         OC.sub.4 H.sub.9 iso                                                                             n.sub.D.sup.25 1.5538                              9         OCH(CH.sub.3)C.sub.3 H.sub.7 n                                       10        OCH(CH.sub.3 (C.sub.5 H.sub.11 n                                     11        OC.sub.8 H.sub.17 n                                                  12        OC.sub.2 H.sub.4 OCH.sub.3                                                                       n.sub.D.sup.25 1.5547                              13        OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                    14        OC.sub.2 H.sub.4 Cl                                                                              n.sub.D.sup.25 1.5722                              15        OC.sub.2 H.sub. 4 Br                                                 16                                                                                        ##STR12##        n.sub.D.sup.30 1.5617                              17                                                                                        ##STR13##                                                           18                                                                                        ##STR14##        n.sub.D.sup.30 1.5565                              19        OCH.sub.2 CHCH.sub.2                                                                             n.sub.D.sup.25 1.5629                              20        OC.sub.2 H.sub.4CHCH.sub.2                                           21        OCH.sub.2 C(CH.sub.3)CH.sub.2                                        22        OCH.sub.2 CCH     m.p. 64-68°                                 23        OCH(CH.sub.3)CCH                                                     24                                                                                        ##STR15##                                                           25                                                                                        ##STR16##                                                           26        OCH.sub.2 CN                                                         27        OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                                              n.sub.D.sup.30 1.5445                              28        SCH.sub.3         n.sub.D.sup.25 1.5850                              29        SC.sub.2 H.sub.5                                                     30        SC.sub.3 H.sub.7 n                                                   31        SC.sub.3 H.sub.7 iso                                                 32        SC.sub.4 H.sub.9 iso                                                 33        SCH.sub.2 CHCH.sub.2                                                 34        SCH.sub.2CHCHCH.sub.3                                                35        SCH.sub.2 COOCH.sub.3                                                                            n.sub.D.sup.40 1.5788                              36                                                                                        ##STR17##                                                           37        O.sup.⊖ Na.sup.⊕                                                                     m.p. 98-101                                        38        O.sup.⊖ NH.sub.4.sup.⊕                                   39        NH.sub.2          m.p. 142-5°                                 40        N(CH.sub.3).sub.2                                                    41        NHC.sub.2 H.sub.5 m.p. 112-5°                                 42        NHC.sub.2 H.sub.4 OH                                                 43        NH(CH.sub.2).sub.3 OCH.sub.3                                                                     m.p. 90-92°                                 44        NHC.sub.2 H.sub.4 OCH.sub.3                                                                      m.p. 89-91°                                 45        NHC.sub.2 H.sub.4 Cl                                                 46        NHCH.sub.2 CHCH.sub.2                                                                            m.p. 119-120°                               47        N(CH.sub.2 CHCH.sub.2).sub.2                                         48        NHC.sub.3 H.sub.7 iso                                                49        N(C.sub.2 H.sub.5).sub.2                                                                         m.p. 73-4°                                  50        NHC.sub.4 H.sub.9 n                                                  51        NHC.sub.5 H.sub.11 iso                                               52                                                                                        ##STR18##                                                           53                                                                                        ##STR19##        m.p. 39-42°                                 54        NHCH.sub.2 COOC.sub.2 H.sub.5                                        55        N(CH.sub.3)OCH.sub.3                                                                             m.p. 75-7°                                  56        ONC(CH.sub.3).sub.C.sbsb.2.sub.H.sbsb.5                              57        ONC(CH.sub.3).sub.2                                                  58                                                                                        ##STR20##                                                           ______________________________________                                          ##STR21##                                                                     No.         B               phys. data                                         ______________________________________                                         59        OCH.sub.3                                                            60        OC.sub.2 H.sub.5                                                     61        OCH.sub.2CHCH.sub.2                                                  62        OC.sub.3 H.sub.6 OCH.sub.3                                           63        SCH.sub.3                                                            64        SCH.sub.2 CCH                                                        65        NH CH.sub.3                                                          66        N(CH.sub.3)OCH.sub.3                                                                             n.sub.D.sup.30 1.5613                              ______________________________________                                          ##STR22##                                                                     No.         B               phys. data                                         ______________________________________                                         67        OCH.sub.3         m.p. 88-89°                                 68        OC.sub.2 H.sub.5  n.sub.D.sup.30 1.5620                              69        OC.sub.3 H.sub.7 iso                                                                             n.sub.D.sup.30 1.5563                              70        OC.sub.4 H.sub.9 iso                                                 71        OC.sub.2 H.sub.4 OCH.sub.3                                           72        OCH.sub.2 CN                                                         73        ONC(CH.sub.3).sub.2                                                  74        OCH.sub.2 COOCH.sub.3                                                75        SCH.sub.3                                                            76        SC.sub.3 H.sub.7 iso                                                 77        SC.sub.5 H.sub.11 n                                                  78        NH.sub.2                                                             79        NHC.sub.2 H.sub.5 m.p. 104-5°                                 80        N(C.sub.2 H.sub.5).sub.2                                             81        NHCH.sub.3                                                           82        NHCH.sub.2 CHCH.sub.2                                                83        NHCH.sub.2 CCH                                                       84        N(CH.sub.3)OCH.sub.3                                                                             n.sub.D.sup.25 1.5660                              85                                                                                        ##STR23##                                                           86                                                                                        ##STR24##                                                           ______________________________________                                          ##STR25##                                                                     No.         B               phys. data                                         ______________________________________                                         87        OCH.sub.3         m.p. 107-8°                                 88        OC.sub.2 H.sub.5                                                     89        OC.sub.3 H.sub.7 n                                                   90        OC.sub.3 H.sub.7 iso                                                                             n.sub.D.sup.30 1.5638                              91        OC.sub.4 H.sub.9 n                                                   92        OC.sub.4 H.sub.9 sec.                                                                            n.sub.D.sup.30 1.5630                              93        OCH(CH.sub.3)C.sub.4 H.sub.9 n                                       94        OC.sub.8 H.sub.17 n                                                  95        OC.sub.2 H.sub.4 OCH.sub.3                                                                       n.sub.D.sup.30 1.5709                              96        OCH(CH.sub.3)COOCH.sub.3                                             97        OC.sub.2 H.sub.4 Cl                                                  98        OCH.sub.2 CHCH.sub.2                                                                             n.sub.D.sup.30 1.5771                              99        OCH.sub.2 C(CH.sub.3)CH.sub.2                                        100       OCH.sub.2 CCH                                                        101                                                                                       ##STR26##                                                           102       OCH(CH.sub.3)CCH                                                     103       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                               n.sub.D.sup.40 1.5699                              104                                                                                       ##STR27##                                                           105                                                                                       ##STR28##                                                           106       SCH.sub.3                                                            107       SC.sub.2 H.sub.5                                                     108       SC.sub.4 H.sub.9 iso                                                 109       SCH.sub.2 CHCH.sub.2                                                 110       SCH.sub.2 C(CH.sub.3)CH.sub.2                                                                    n.sub.D.sup.30 1.5920                              111       SCH.sub.2 CCH     m.p. 92-95°                                 112       NH.sub.2          m.p. 135-7°                                 113       NHCH.sub.3        m.p. 126-7°                                 114       N(CH.sub.3).sub.2 m.p. 116-7°                                 115       NHC.sub.2 H.sub.5 m.p. 128-9°                                 116       N(C.sub.2 H.sub.5).sub.2                                                                         m.p. 88-9°                                  117       NHC.sub.3 H.sub.7 n                                                                              m.p. 112-4°                                 118       NHC.sub.3 H.sub.7 iso                                                                            m.p. 112-3°                                 119       NHCH.sub.2 CHCH.sub.2                                                                            m.p. 108-11°                                120       N(CH.sub.2 CHCH.sub.2).sub.2                                                                     n.sub.D.sup.30 1.5760                              121       NHCH.sub.2 CCH    m.p. 148-150°                               122       NHC.sub.4 H.sub.9 n                                                  123       NHC.sub.4 H.sub.9 sec.                                               124       NHC.sub.4 H.sub.9 iso                                                125       NHC.sub.5 H.sub.11 iso                                                                           m.p. 95-98°                                 126       NHC.sub.6 H.sub.13 n                                                                             m.p. 87-90°                                 127       NHC.sub.2 H.sub.4 OCH.sub.3                                                                      m.p. 101-3°                                 128       NH(CH.sub.3)OCH.sub.3                                                                            m.p. 93-4°                                  129       NHC(CH.sub.3).sub.2 CCH                                                                          m.p. 118-120°                               130       NHCH.sub.2 COOC.sub.2 H.sub.5                                        131                                                                                       ##STR29##        m.p. 116-8°                                 132                                                                                       ##STR30##        m.p. 118-120°                               133                                                                                       ##STR31##        m.p. 113-116°                               134                                                                                       ##STR32##        m.p. 132-134°                               135                                                                                       ##STR33##        m.p. 130- 132°                              136                                                                                       ##STR34##                                                           137                                                                                       ##STR35##        m.p. 148-151°                               138                                                                                       ##STR36##        m.p. 134-137°                               139                                                                                       ##STR37##        m.p. 117-119°                               140       NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                   141       NHC.sub.3 H.sub.6 OCH.sub.3                                                                      n.sub.D.sup.40 1.5738                              142       NHC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                   143       NHC.sub.8 H.sub.17 n                                                 144       OH                m.p. 134-6°                                 145       O.sup. ⊖ NH.sub.3 C.sub.3 H.sub.7 iso                        146       ONC (CH.sub.3).sub.2                                                 ______________________________________                                          ##STR38##                                                                     No.         B               phys. data                                         ______________________________________                                         147       OH                                                                   148       OCH.sub.3         m.p. 80-2°                                  149       OC.sub.2 H.sub.5  n.sub.D.sup.25 1.5511                              150       OC.sub.3 H.sub.7 n                                                   151       OC.sub.3 H.sub.7 iso                                                                             n.sub.D.sup.30 1.5585                              152       OC.sub.4 H.sub.9 n                                                   153       OC.sub.4 H.sub.9 sec.                                                                            n.sub.D.sup.30 1.5590                              154       OC.sub.2 H.sub.4 Cl                                                  155       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                                               n.sub.D.sup.30 1.5715                              156                                                                                       ##STR39##                                                           157       OC.sub.2 H.sub.4 OCH.sub.3                                           158       OC.sub.3 H.sub.6 OCH.sub.3                                           159       OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                  160       OCH.sub.2 CN                                                         161       OCH(CH.sub.3)COOC.sub.2 H.sub.5                                                                  n.sub.D.sup.30 1.5525                              162       ONC(CH.sub.3).sub.2                                                                              n.sub.D.sup.30 1.5665                              163       OCH.sub.2 CHCH.sub.2                                                                             n.sub.D.sup.30 1.5735                              164       OCH.sub.2 CHCHCH.sub.3                                               165       OCH(CH.sub.3)CHCH.sub.2                                              166       OCH.sub.2 CCH     n.sub.D.sup.30 1.5795                              167       OC(CH.sub.3).sub.2 CCH                                               168                                                                                       ##STR40##                                                           169                                                                                       ##STR41##                                                           170                                                                                       ##STR42##        m.p. 145-7°                                 171                                                                                       ##STR43##                                                           172       SCH.sub.3         n.sub.D.sup.30 1.6015                              173       SC.sub. 2 H.sub.5 n.sub.D.sup.30 1.5933                              174       SC.sub.4 H.sub.9 iso                                                 175       SCH.sub.2 COOCH.sub.3                                                176       NH.sub.2          m.p. 156-9°                                 177       NHCH.sub.3        m.p. 132-4°                                 178       N(CH.sub.3).sub.2 m.p. 118-120°                               179       NHC.sub.2 H.sub.5                                                    180       N(C.sub.2 H.sub.5).sub.2                                             181       NHC.sub.3 H.sub.7 iso                                                182                                                                                       ##STR44##                                                           183       NHCH.sub.2 COOCH.sub.3                                               184                                                                                       ##STR45##                                                           185                                                                                       ##STR46##                                                           186       NHC.sub.2 H.sub.4 OCH.sub.3                                                                      m.p. 118-120°                               187       NHC.sub.3 H.sub.6 OCH.sub.3                                                                      m.p. 90-92°                                 188       NHCH.sub.2 CHCH.sub.2                                                                            m.p. 104-6°                                 189       N(CH.sub.2 CHCH.sub.2).sub.2                                         190       N(CH.sub.3)OCH.sub.3                                                                             n.sub.D.sup.30 1.5800                              191       NHOCH.sub.2 CHCH.sub.2                                               ______________________________________                                          ##STR47##                                                                     No.          B              phys. data                                         ______________________________________                                         192       OCH.sub.3         m.p. 75°                                    193       OC.sub.2 H.sub.5                                                     194       OC.sub.3 H.sub.7 iso                                                                             m.p. 60-3°                                  195       OCH(CH.sub.3)C.sub.3 H.sub.7 n                                                                   n.sub.D.sup.30 1.5561                              196       OC.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                                n.sub.D.sup.30 1.5631                              197       OC.sub.2 H.sub.4 Cl                                                                              n.sub.D.sup.30 1.5792                              198       OC.sub.8 H.sub.17 n                                                                              n.sub.D.sup.30 1.5458                              199       OCH.sub.2 CHCHCH.sub.3                                                                           n.sub.D.sup.30 1.5730                              200       OCH.sub.2 CCH     m.p. 80-82°                                 201                                                                                       ##STR48##        n.sub.D.sup.30 1.5811                              202       SC.sub.3 H.sub.7 iso                                                                             n.sub.D.sup.30 1.5795                              203       SC.sub.4 H.sub.9 iso                                                                             n.sub.D.sup.30 1.5805                              204       SCH.sub.2 COOCH.sub.3                                                                            n.sub.D.sup.30 1.5780                              205       SCH(CH.sub.3)C.sub.2 H.sub.5                                                                     n.sub.D.sup.30 1.5778                              206       NH.sub.2          m.p. 155-156°                               207       NHC.sub.2 H.sub.5 m.p. 114-115°                               208       N(CH.sub.3)OCH.sub.3                                                 209       OH                m.p. 150-1°                                 ______________________________________                                          ##STR49##                                                                     No.          B              phys. data                                         ______________________________________                                         210       OCH.sub.3         m.p. 74-77°                                 211       OC.sub.2 H.sub.5                                                     212       OC.sub.3 H.sub.7 n                                                   213       OC.sub.3 H.sub.7 iso                                                 214       OC.sub.4 H.sub.9 iso                                                 215       OC.sub.6 H.sub.13 n                                                  216       OC.sub.2 H.sub.4 Cl                                                  217       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                   218       OC.sub.2 H.sub.4 OC.sub.4 H.sub.9                                    219                                                                                       ##STR50##                                                           220                                                                                       ##STR51##                                                           221                                                                                       ##STR52##                                                           222       OCH.sub.2 CHCH.sub.2                                                 223       OCH(CH.sub.3)CHCH.sub.2                                              224       OCH.sub.2 CCH                                                        225       OCH(CH.sub.2)CCH                                                     226       SCH.sub.3                                                            227       SCH.sub.2 CHCH.sub.2                                                 228       SCH(CH.sub.3)CHCH.sub.2                                              229       SCH.sub.2 CCH                                                        230                                                                                       ##STR53##                                                           231                                                                                       ##STR54##                                                           232       OH                                                                   233       O.sup.⊖ H.sub.3 N.sup.⊕ (C.sub.3 H.sub.7 iso).sub.2      234       O.sup.⊖ Na.sup.⊕                                         235       O.sup.⊖ NH.sub.4.sup.⊕                                   236       NH.sub.2                                                             237       NHCH.sub.3                                                           238       N(C.sub.2 H.sub.5).sub.2                                             239       NHC.sub.4 H.sub.9 iso                                                240       NHC.sub.2 H.sub.4 OCH.sub.3                                          241       NHC.sub.3 H.sub.6 OC.sub.2 H.sub.5                                   242       N(CH.sub.3)OCH.sub.3                                                 ______________________________________                                          ##STR55##                                                                     No.         B               phys. data                                         ______________________________________                                         243       OH                                                                   244       OCH.sub.3                                                            245       OC.sub.3 H.sub.7 iso                                                 246       OC.sub.4 H.sub.9 n                                                   247       SCH.sub.3                                                            248       SCH.sub.2CHCH.sub.2                                                  249       SCH.sub.2 COOCH.sub.3                                                250       SC.sub.2 H.sub.4 OCH.sub.3                                           251       SC.sub.4 H.sub.9 iso                                                 252                                                                                       ##STR56##                                                           253                                                                                       ##STR57##                                                           254       NH.sub.2                                                             255       NHC.sub.2 H.sub.5                                                    256       N(CH.sub.3).sub.2                                                    257       NHCH.sub.2 CHCH.sub.2                                                258       N(CH.sub.3)OCH.sub.3                                                 259       NHC.sub. 5 H.sub.11 n                                                ______________________________________                                          ##STR58##                                                                     No.         B               phys. data                                         ______________________________________                                         260       OH                                                                   261       OCH.sub.3         n.sub.D.sup.25 1.5150                              262       OC.sub.2 H.sub.5                                                     263       OC.sub.3 H.sub.7 n                                                   264       OC.sub.3 H.sub.7 iso                                                 265       OCH.sub.2 CHCH.sub.2                                                 266       OCH.sub.2 C CH                                                       267       OCH(CH.sub.3)COOC.sub.2 H.sub.5                                      268       NH.sub.2                                                             269       NHCH.sub.3                                                           270       N(CH.sub.3).sub.2                                                    271       N(C.sub.3 H.sub.7 iso).sub.2                                         272       NHCH.sub.2 CHCH.sub.2                                                273       NHCH.sub.2 CHCH                                                      ______________________________________                                          ##STR59##                                                                     No.         B               phys. data                                         ______________________________________                                         274       OH                                                                   275       OCH.sub.3         m.p. 74-75°                                 276       OC.sub.2 H.sub.5                                                     277       OCH.sub.2 CN                                                         278       OC.sub.3 H.sub.7 n                                                   279       OC.sub.3 H.sub.7 iso                                                 280       OC.sub.4 H.sub.9 n                                                   281       OCH.sub.2 CHCH.sub.2                                                 282       OCH.sub.2 CHCHCH.sub.3                                               283       OCH.sub.2 CCH                                                        284       SCH.sub.3                                                            285       SC.sub.2 H.sub.5                                                     286       SC.sub.3 H.sub.7 iso                                                 287       SCH.sub.2 CN                                                         288       SCH.sub.2 COOCH.sub.3                                                289       NH.sub.2                                                             290       NHCH.sub.3                                                           291       N(CH.sub.3).sub.2                                                    292       NH(C.sub.3 H.sub.7 iso)                                              293       NHCH.sub.2 CHCH.sub.2                                                294                                                                                       ##STR60##                                                           ______________________________________                                          ##STR61##                                                                     No.         B               phys. data                                         ______________________________________                                         295       OH                                                                   296       OCH.sub.3                                                            297       OC.sub.2 H.sub.5  n.sub.D.sup.30 1.5223                              298       OC.sub.3 H.sub.7 n                                                   299       OC.sub.4 H.sub.9 iso                                                 300       OCH.sub.2 CHCH.sub.2                                                 301       OCH.sub.2 CCH                                                        302       OCH(CH.sub.3)CCH                                                     303       OC.sub.4 H.sub.9 n                                                   304       OC.sub.4 H.sub.9 tert.                                               305       OC.sub.4 H.sub.9 sec.                                                306       OC.sub.2 H.sub.4 OCH.sub.3                                           307       OC.sub.2 H.sub.4 OC.sub.4 H.sub.9 n                                  308       OC.sub.2 H.sub.4 Cl                                                  309       OC.sub.2 H.sub.4 Br                                                  310       OCH.sub.2 CHCHCH.sub.2 Cl                                            311       OCH.sub.2 C(CH.sub.3)CH.sub.2                                        312       OC.sub.2 H.sub.4 N(CH.sub.3).sub.2                                   313       OC.sub.2 H.sub.4 N(C.sub.2 H.sub.5).sub.2                            314       OCH(CH.sub.3)COOC.sub.2 H.sub.5                                      315       OCH(C.sub.2 H.sub.5).sub.2                                           316       SH                                                                   317       SCH.sub.3                                                            318       SC.sub.2 H.sub.5                                                     319       SCH.sub.2 COOC.sub.2 H.sub.5                                         320       SCH.sub.2 CHCH.sub.2                                                 321       SCH.sub.2 CCH                                                        322       SC.sub.4 H.sub.9 n                                                   323       SCH.sub.2CH(CH.sub.3)CH.sub.2                                        324       SCH(CH.sub.3)CCH                                                     325       NH.sub.2          m.p. 127-128°                               326       NHC.sub.2 H.sub.4 OCH.sub.3                                          327       NHC.sub.3 H.sub.6 OCH.sub.3                                          328       N(C.sub.2 H.sub.4 OH).sub.2                                          329       NHC.sub.2 H.sub.4 COOCH.sub.3                                        330       NHCH.sub.2 COOCH.sub.3                                               331       NHC.sub.2 H.sub.4 OH                                                 332       NHCH.sub.3        m.p. 113-114°                               333       N(CH.sub.3).sub.2                                                    334       NHC.sub.2 H.sub.5                                                    335       N(C.sub.2 H.sub.5).sub.2                                             336       NHC.sub.3 H.sub.7 n                                                  337       NHC.sub.4 H.sub.9 n                                                  338                                                                                       ##STR62##                                                           339       N(CH.sub.3)OCH.sub.3                                                 ______________________________________                                          ##STR63##                                                                     No.          B              phys. data                                         ______________________________________                                         340       OH                                                                   341       OCH.sub.3         m.p. 89-93°                                 342       OC.sub.2 H.sub.5  n.sub.D.sup.20 1.5340                              343       OCH.sub.2 CHCH.sub.2                                                 344       SCH.sub.2 CHCH.sub.2                                                 345       SCH.sub.3                                                            346       SCH.sub.2 COOCH.sub.3                                                347       NH.sub.2                                                             348       NHCH.sub.3                                                           349       N(CH.sub.3).sub.2                                                    350       NHC.sub.2 H.sub.5                                                    351       NHCH.sub.2 CHCH.sub.2                                                ______________________________________                                          ##STR64##                                                                     No.         B               phys. data                                         ______________________________________                                         352       OH                                                                   353       OCH.sub.3                                                            354       OC.sub.2 H.sub.5  n.sub.D.sup.30 1.5167                              355       OC.sub.3 H.sub.7 iso                                                 356       OC.sub.2 H.sub.4 OCH.sub.3                                           357       OCH.sub.2 CHCH.sub.2                                                 358       OCH.sub.2 CH                                                         359       SCH.sub.3                                                            360       SC.sub.2 H.sub.5                                                     361       SCH.sub.2 CHCH.sub.2                                                 362       NH.sub.2                                                             363       N(CH.sub.3).sub.2                                                    364       NHC.sub.2 H.sub.5                                                    365       NHC.sub.2 H.sub.4 OCH.sub.3                                          366       N(CH.sub.3)OCH.sub.3                                                 ______________________________________                                          ##STR65##                                                                     No.   E      D      Z      B        phys. data                                 ______________________________________                                         367   Cl     Br     Cl   OCH.sub.3                                             368   Cl     Br     Cl   OC.sub.2 H.sub.5                                      369   I      H      NO.sub.2                                                                            OCH.sub.3  n.sub.D.sup.25 1.6125                      370   I      H      Cl   OCH.sub.3  n.sub.D.sup.25 1.5995                      371   Br     Br     NO.sub.2                                                                            OCH.sub.3  m.p. 118-120°                       372   CN     Cl     Cl   OCH.sub.3  m.p. 109-111°                       373   Br     CN     Cl   OCH.sub.3  m.p. 135-7°                         374   Cl     H      Cl   OCH.sub.3  b.p. 145- 150°/0.04                 375   Cl     H      NO.sub.2                                                                            NH.sub.2                                              376   Br     H      NO.sub.2                                                                            OC.sub.2 H.sub.5                                      377   Br     H      Cl   OCH.sub.2 CHCH.sub.2                                  378   CN     Cl     Br   OCH.sub.3  m.p. 107-9°                         379   CF.sub.3                                                                              Cl     Br   OCH.sub.3                                             380   Cl     CH.sub.3                                                                              Cl   OCH.sub.3                                             381   Cl     CH.sub.3                                                                              Br   OC.sub.2 H.sub.5                                      382   Cl     CH.sub.3                                                                              NO.sub.2                                                                            OCH.sub.3                                             383   Cl     CH.sub.3                                                                              NO.sub.2                                                                            NHCH.sub.3                                            384   CF.sub.3                                                                              H      Br   OCH.sub.3                                             385   CF.sub.3                                                                              Br     Cl   OCH.sub.3                                             386   Br     Br     Br   OCH.sub.3  m.p. 64-6°                          387   Br     Br     NO.sub.2                                                                            OCH.sub.3  m.p. 118-120°                       388   Br     Br     Br   SCH.sub.3                                             389   Br     Br     Cl   OCH.sub.3  m.p. 86-8°                          390   Cl     H      Br   OCH.sub.3  m.p. 80-2°                          391   CF.sub.3                                                                              Br     NO.sub.2                                                                            NH.sub.2                                              392   CF.sub.3                                                                              Br     NO.sub.2                                                                            NHCH.sub.3                                            ______________________________________                                          ##STR66##                                                                     No.   E      D      Z      B        phys. data                                 ______________________________________                                         393   Cl     Br     NO.sub.2                                                                            OC.sub.2 H.sub.5                                                                          n.sub.D.sup.25 1.5820                      394   CN     Cl     NO.sub.2                                                                            OC.sub.2 H.sub.5                                      395   Cl     CH.sub.3                                                                              NO.sub.2                                                                            OC.sub.2 H.sub.5                                      396   Cl     CH.sub.3                                                                              NO.sub.2                                                                            NH.sub.2                                              397   Br     Br     NO.sub.2                                                                            OC.sub.2 H.sub.5                                      398   CF.sub.3                                                                              Br     NO.sub.2                                                                            OC.sub.2 H.sub.5                                      ______________________________________                                          ##STR67##                                                                     No.   E      D      Z      B        phys. data                                 ______________________________________                                         399   Cl     Cl     NO.sub.2                                                                            OCH.sub.3  m.p. 83-5°                          400   Cl     Cl     NO.sub.2                                                                            NH.sub.2   m.p. 203-5°                         401   Cl     Cl     NO.sub.2                                                                            NHC.sub.2 H.sub.5                                                                         m.p. 124-5°                         402   Cl     Cl     NO.sub.2                                                                            N(CH.sub.3)OCH.sub.3                                                                      m.p. 106-7°                         403   Cl     Cl     NO.sub.2                                                                            OC.sub.2 H.sub.4 OCH.sub.3                                                                m.p. 71-2°                          404   Cl     Cl     Br   OCH.sub.3  m.p. 81-2°                          405   Cl     CH.sub.3                                                                              NO.sub.2                                                                            OCH.sub.3                                             406   CF.sub.3                                                                              Cl     NO.sub.2                                                                            OCH.sub.3                                             407   CF.sub.3                                                                              H      NO.sub.2                                                                            OCH.sub.2 CHCH.sub.2                                  408   CF.sub.3                                                                              H      Cl   OCH.sub.3                                             409   CF.sub.3                                                                              Cl     Cl   OCH.sub.3                                             ______________________________________                                          ##STR68##                                                                     No.   E      D      Z      B        phys. data                                 ______________________________________                                         410   Cl     Cl     Cl   OCH.sub.3  n.sub.D.sup.30 1.5586                      411   Cl     Cl     NO.sub.2                                                                            OCH.sub.3  n.sub.D.sup.30 1.5527                      412   Cl     Cl     NO.sub.2                                                                            OC.sub.2 H.sub.5                                      413   Cl     Cl     NO.sub.2                                                                            NHCH.sub.3                                            414   CF.sub. 3                                                                             H      NO.sub.2                                                                            OCH.sub.3                                             415   CF.sub.3                                                                              Cl     NO.sub.2                                                                            OC.sub.2 H.sub.5                                      416   CF.sub.3                                                                              Cl     Cl   OCH.sub.3                                             417   Br     Br     NO.sub.2                                                                            OCH.sub.3                                             ______________________________________                                          ##STR69##                                                                     No.         B               phys. data                                         ______________________________________                                         418       OCH.sub.3         m.p. 93-94°                                 419       OC.sub.2 H.sub.5                                                     420       OC.sub.2 H.sub.4 OCH.sub.3                                           421       NH.sub.2          m.p. 145-146°                               422       NHCH.sub.3        m.p. 132-134°                               423       N(CH.sub.3).sub.2 m.p. 136-137°                               424       NHC.sub.2 H.sub.5 m.p. 124-126°                               425       N(C.sub.2 H.sub.5).sub.2                                                                         m.p. 75-77°                                 ______________________________________                                          ##STR70##                                                                     No.   E      D      Z    R.sub.1                                                                             A         phys. data                             ______________________________________                                         426   Cl     Cl     NO.sub.2                                                                            H    CN        m.p. 118-120°                   427   Cl     Cl     Cl   CH.sub.3                                                                            CN        m.p. 119-120°                   428   Cl     Cl     Cl   H    CN        m.p. 101-3°                     429   Cl     Cl     Cl   CH.sub.3                                                                             ##STR71##                                                                               m.p. 133-5°                     430   Cl     Cl     Cl   CH.sub.3                                                                             ##STR72##                                       431   Cl     Cl     NO.sub.2                                                                            CH.sub.3                                                                             ##STR73##                                       ______________________________________                                    

The compositions of the present invention are obtained in known manner by homogeneously mixing and grinding active substances of the general formula I with suitable carriers, with or without the addition of dispersants or solvents which are inert to the active substances. The active substances can be processed to the following formulations:

solid formulations:

dusts, tracking powders, granules (coated granules, impregnated granules and homogeneous granules);

active substance concentrates which are dispersible in water:

wettable powders, pastes, emulsions;

liquid formulations: solutions.

The concentration of active substance in the above described compositions is between 0.1 and 95%, preferably between 1 and 80%. The rates of application are ordinarily from 0.1 to 10 kg, preferably from 0.25 to 5 kg, of active substance per hectare. The compositions of the present invention can also be mixed with other biocidal active substances or compositions.

The active substances of the formula I can be formulated for example as follows (parts are by weight):

Dusts

The following substances are used to prepare

(a) 5% and (b) a 2% dust:

(a)

5 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid methyl ester,

95 parts of talc;

(b)

2 parts of active substance

1 part of highly dispersed silicic acid

97 parts of talc.

The active substances are mixed with the carriers and ground.

Granulate

The following substances are used to prepare a 5% granulate:

5 parts of the above active substance

0.25 parts of epichlorohydrin

0.25 parts of cetyl polyglycol ether

3.25 parts of polyethylene glycol

91 parts of kaolin (particle size 0.3-0.8 mm).

The active substance is mixed with epichlorohydrin and the mixture is dissolved in 6 parts of acetone. Then polyethylene glycol and cetyl polyglycol ether are added. The resulting solution is sprayed on kaolin and subsequently evaporated in vacuo.

Wettable Powders

The following constituents are used to prepare

(a) a 50%, (b) a 25% and (c) a 10% wettable powder:

(a)

50 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-bromophenoxy] propionic acid methyl ester

5 parts of sodium dibutylnaphthylsulphonate

3 parts of naphthalenesulphonic acid/phenolsulphonic acid/formaldehyde condensate (3:2:1)

20 parts of kaolin

22 parts of Champagne chalk;

(b)

25 parts of the above active substance

5 parts of sodium oleylmethyltauride

2.5 parts of naphthalenesulphonic acid/formaldehyde condensate

0.5 parts of carboxymethyl cellulose

5 parts of neutral potassium aluminium silicate

62 parts of kaolin;

(c)

10 parts of the above active substance

3 parts of a mixture of the sodium salts of saturated fatty alcohol sulphates

5 parts of naphthalenesulphonic acid/formaldehyde condensate

82 parts of kaolin.

The indicated active substance is applied to the corresponding carriers (kaolin and chalk) and then these are mixed and ground, to yield wettable powders of excellent wettability and suspension power. By diluting these wettable powders with water it is possible to obtain suspensions of the desired concentration of active substance. Such suspensions are used for controlling weeds and grass-like weeds in crops of cultivated plants by the preemergent method and for treating areas of grass.

Paste

The following substances are used to manufacture a 45% paste:

45 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-nitrophenoxy] propionic acid methyl ester

5 parts of sodium aluminum silicate

14 parts of cetyl polyglycol ether with 8 moles of the ethylene oxide

1 part of oleyl polyglycol ether with 5 moles of the ethylene oxide

2 parts of spindle oil

10 parts of polyethylene glycol

23 parts of water.

The active substance is homogeneously mixed with the adjuvants in appropriate devices and ground, yielding a paste from which, by dilution with water, it is possible to obtain suspensions of the desired concentration of active substance. The suspensions are suitable for treating areas of grass.

Emulsifiable Concentrate

The following ingredients are mixed to manufacture a 25% emulsifiable concentrate:

25 parts of α-[3-(3',5'-dichloropyridyl-2'-oxy)-6-chlorophenoxy] propionic acid isopropyl ester

5 parts of a mixture of nonylphenolpolyoxyethoxy-ethylene and calcium dodecylenesulphonate

35 parts of 3,3,5-trimethyl-2-cyclohexan-1-one

35 parts of dimethyl formamide.

This concentrate can be diluted with water to give emulsions in the desired concentrations.

Instead of using the respective active substance indicated in the foregoing formulation examples, it is also possible to use another of the compounds comprised by the formula I.

The active substances of the invention are also of interest for combination with an number of hercides of the phenylurea and triazine series for use in cereal crops, maize, sugar cane, and in fruit culture and viticulture.

The active substances of the formula I are distinguished by a very pronounced preemergent herbicidal action and are thus also strong germination inhibitors.

The following test methods were employed to established the usefulness of the compounds of the formula I as herbicides (pre- and postemergent).

Preemergent herbicidal action (germination inhibition)

In a greenhouse, immediately after sowing the test plants in seed dishes the surface of the soil is treated with an aqueous suspension of the active substances obtained from a 25% wettable powder. A concentration was used, which corresponded to 4 kg of active substance per hectare. The seed dishes are then kept in the greenhouse at 22°-25° C. and 50 to 70% relative humidity. The test was evaluated 3 weeks later according to the following rating:

1=plants have not germinated or are totally withered

2-8=intermediate stages of damage

9=plants undamaged (as untreated control).

The results are resumed in the table below:

    ______________________________________                                         Compound           Sinapis  Setaria                                                                               Stellaria                                   number    oats     alba     italica                                                                               media                                       ______________________________________                                          2        8        3        2      2                                            14       9        2        2      3                                            35       9        4        1      2                                            53       7        3        2      2                                            87       2        1        1      3                                           112       2        1        1      1                                           114       1        2        1      2                                           115       1        1        1      1                                           127       2        2        1      2                                           144       9        1        1      5                                           149       7        2        2      2                                           192       9        2        1      1                                           201       9        4        1      1                                           210       2        1        1      1                                           261       2        2        1      7                                           297       1        1        1      1                                           399       3        1        3      9                                           418       9        1        1      1                                           ______________________________________                                    

Post-emergent herbicidal action (Contact herbicide)

A number of weeds and cultivated plants, both mono- and dicotyledonous, were sprayed after emergence in the 4- to 6-leaf stage with an aqueous active substance emulsion in a rate of 4 kg of active substance per hectare and kept at 24°-26° C. and 45-60% relative humidity. The test was evaluated, as in the preemergent test, 15 days after treatment in accordance with the same rating.

The results are resumed in the table below:

    ______________________________________                                         Compound         Setaria  Lolium Sinapis                                                                               Stellaria                              No.     oats     italica  perenne                                                                               alba   media                                  ______________________________________                                          1      2        1        1      1      1                                       2      4        1        2      1      1                                       3      4        1        3      2      2                                       12     7        1        3      1      2                                       16     6        2        3      1      2                                       19     5        1        3      1      2                                       22     6        2        6      2      1                                       27     4        1        2      1      1                                       28     6        1        5      3      2                                       35     5        1        3      1      1                                       41     4        5        4      2      2                                       43     4        1        4      1      1                                       53     5        2        6      1      2                                       55     6        1        3      1      1                                       66     4        1        4      2      3                                       92     2        1        1      1      3                                       95     4        2        3      1      6                                       98     4        1        1      1      2                                      111     4        2        2      1      2                                      113     2        2        2      2      3                                      115     2        2        5      1      5                                      128     2        1        3      1      1                                      129     7        1        6      1      6                                      141     4        3        4      1      4                                      149     2        1        2      1      1                                      192     3        1        1      1      1                                      194     3        1        1      1      1                                      196     3        1        1      1      1                                      200     4        1        2      1      1                                      201     7        1        3      1      1                                      202     6        2        4      2      2                                      204     5        2        3      2      2                                      210     1        1        1      1      1                                      261     1        1        1      1      1                                      297     1        1        1      1      1                                      372     4        2        4      2      1                                      387     2        1        1      1      1                                      399     1        1        2      1      3                                      403     2        1        2      1      8                                      418     4        1        2      1      4                                      426     2        1        3      1      4                                      ______________________________________                                     

We claim:
 1. A compound of the formula ##STR74## wherein R₃ is hydrogen; an alkali metal cation; ammonium; a C₁ -C₄ alkyl ammonium cation whose alkyl moiety is optionally substituted by hydroxy or C₁ -C₄ alkoxy; C₁ -C₁₈ alkyl optionally substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxycarbonyl or C₃ -C₈ cycloalkyl; C₃ -C₁₀ alkenyl optionally substituted by halogen; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; phenyl optionally substituted by halogen or C₁ -C₄ alkoxy; or benzyl optionally ring substituted by halogen.
 2. A compound of the formula ##STR75## wherein R₃ is hydrogen; an alkali metal cation; ammonium; a C₁ -C₄ alkyl ammonium cation whose alkyl moiety is optionally substituted by hydroxy or C₁ -C₄ alkoxy; C₁ -C₁₈ alkyl optionally substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxycarbonyl or C₃ -C₈ cycloalkyl; C₃ -C₁₀ alkenyl optionally substituted by halogen; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; phenyl optionally substituted by halogen or C₁ -C₄ alkoxy; or benzyl optionally ring substituted by halogen.
 3. A compound of the formula ##STR76## wherein R₃ is hydrogen; an alkali metal cation; ammonium; a C₁ -C₄ alkyl ammonium cation whose alkyl moiety is optionally substituted by hydroxy or C₁ -C₄ alkoxy; C₁ -C₁₈ alkyl optionally substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxycarbonyl or C₃ -C₈ cycloalkyl; C₃ -C₁₀ alkenyl optionally substituted by halogen; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; phenyl optionally substituted by halogen or C₁ -C₄ alkoxy; or benzyl optionally ring substituted by halogen.
 4. A compound of the formula ##STR77## wherein R₃ is hydrogen; an alkali metal cation; ammonium; a C₁ -C₄ alkyl ammonium cation whose alkyl moiety is optionally substituted by hydroxy or C₁ -C₄ alkoxy; C₁ -C₁₈ alkyl optionally substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxycarbonyl or C₃ -C₈ cycloalkyl; C₃ -C₁₀ alkenyl optionally substituted by halogen; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; phenyl optionally substituted by halogen or C₁ -C₄ alkoxy; or benzyl optionally ring substituted by halogen.
 5. A compound of the formula ##STR78## wherein R₃ is hydrogen; an alkali metal cation; ammonium; a C₁ -C₄ alkyl ammonium cation whose alkyl moiety is optionally substituted by hydroxy or C₁ -C₄ alkoxy; C₁ -C₁₈ alkyl optionally substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxycarbonyl or C₃ -C₈ cycloalkyl; C₃ -C₁₀ alkenyl optionally substituted by halogen; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; phenyl optionally substituted by halogen or C₁ -C₄ alkoxy; or benzyl optionally ring substituted by halogen.
 6. A compound of the formula ##STR79## wherein R₃ is hydrogen; an alkali metal cation; ammonium; a C₁ -C₄ alkyl ammonium cation whose alkyl moiety is optionally substituted by hydroxy or C₁ -C₄ alkoxy; C₁ -C₁₈ alkyl optionally substituted by halogen, cyano, C₁ -C₈ alkoxy, C₂ -C₈ alkoxycarbonyl or C₃ -C₈ cycloalkyl; C₃ -C₁₀ alkenyl optionally substituted by halogen; C₃ -C₈ alkynyl; C₃ -C₈ cycloalkyl; phenyl optionally substituted by halogen or C₁ -C₄ alkoxy; or benzyl optionally ring substituted by halogen.
 7. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-chlorophenoxy]-propionic acid methyl ester according to claim
 1. 8. α-[3-(3',5'-Dichloropyridinyl-2'-oxy)-6-chlorophenxoy]-propionic acid isopropyl ester according to claim
 1. 9. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoy]-propionic acid methyl ester according to claim
 4. 10. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-nitrophenoxy]-butyric acid ethyl ester according to claim
 5. 11. α-[3-(3',5'-Dichloropyridyl-2'-oxy)-6-bromophenoxy]-propionic acid methyl ester according to claim
 6. 12. A method of controlling weeds at a locus, which comprises applying to said locus a herbicidally effective amount of a compound according to claims 1, 2, 3, 4, 5 or
 6. 13. A herbicidal composition which contains an active ingredient a herbicidally effective amount of a compound according to claims 1, 2, 3, 4, 5 or 6, together with an inert carrier.
 14. A method of controlling weeds at a locus, which comprising applying to said locus a herbicidally effective amount of a compound according to claim
 5. 15. A method of controlling weeds at a locus, which comprising applying to said locus a herbicidally effective amount of the compound according to claim
 10. 